CN109935824A - A kind of expanded graphite negative electrode material and preparation method thereof loading cross acicular tin oxide - Google Patents

A kind of expanded graphite negative electrode material and preparation method thereof loading cross acicular tin oxide Download PDF

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CN109935824A
CN109935824A CN201711351875.6A CN201711351875A CN109935824A CN 109935824 A CN109935824 A CN 109935824A CN 201711351875 A CN201711351875 A CN 201711351875A CN 109935824 A CN109935824 A CN 109935824A
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expanded graphite
tin
negative electrode
oxide
tin oxide
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CN109935824B (en
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晏荦
汤占磊
仰韻霖
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DONGGUAN KAIJIN NEW ENERGY TECHNOLOGY Co Ltd
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DONGGUAN KAIJIN NEW ENERGY TECHNOLOGY Co Ltd
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of expanded graphite negative electrode materials and preparation method thereof for loading cross acicular tin oxide.The preparation method (1) is mainly calcined by expanded graphite dispersion, (2) pink salt and the preparation of structure directing agent mixed solution, the dropwise addition of (3) pink salt and structure directing agent mixed solution, (4) reflux, the reduction of (5) sodium borohydride alkaline solution, (6) filtration washing, (7) medium temperature, the expanded graphite negative electrode material of tin oxide obtained has special appearance structure, has excellent chemical property.

Description

A kind of expanded graphite negative electrode material and preparation method thereof loading cross acicular tin oxide
Technical field
The present invention relates to lithium cell cathode material field more particularly to a kind of expanded graphites for loading cross acicular tin oxide The preparation method of negative electrode material and this material.
Background technique
With signaling for help repeatedly for the non-renewable energy resources such as coal, petroleum, natural gas, energy problem is that the mankind stride into 21 century The severe problem faced, tapping a new source of energy seems most important with renewable and clean energy resource.Lithium ion battery and traditional two Primary cell is compared, and has that operating voltage is high, specific energy is big, discharging voltage balance, has extended cycle life and non-environmental-pollution etc. is prominent Advantage out has been widely used for the miniaturizations electronics such as mobile phone, laptop and Portable Measurement Instrument dress It sets.It is simultaneously also the preferred power supply of following hybrid vehicle and pure power vehicle.
Negative electrode material is one of critical material of lithium ion battery, and the lithium ion battery negative material used is commercialized at present Mainly charcoal class negative electrode material.It has height ratio capacity (200~400mAh/g), low electrode current potential (< 1.0VvsLi+/Li), The advantages that high circulation efficiency (> 95%) and long circulation life.There are carbonaceous mesophase spherules (MCMB), stone in charcoal class negative electrode material Ink and amorphous carbon, wherein graphite material theoretical embedding lithium capacity height, has good layer structure at good conductivity, is in recent years Carry out one of the emphasis of lithium battery research.Graphite material can be divided into artificial graphite and two kinds of natural graphite, natural graphite have than The advantages that surface area is big, specific capacity is high, first charge discharge efficiency is high, but the total insertion of solvent is be easy to cause during charge and discharge, from And lead to its poor circulation.Artificial graphite is lower relative to the degree of graphitization of natural graphite, but it is with high rate performance It is good, with electrolyte good compatibility and the good advantage of stable circulation performance, therefore become research hotspot in recent years.
But due to the limitation of the prior art, current artificial graphite can not greatly improve lithium battery energy density.In order to The energy density of lithium battery is improved, tinbase, silicon substrate and transition metal become negative electrode material and grind because having higher theoretical capacity The mainstream studied carefully.However, volume expansion contraction change is obvious in the lithium intercalation/deintercalation process for these materials, the internal stress of material is big, Material easily ruptures after repeated charge, falls off from collector, the content decline of active material, so as to cause following for material Ring degradation.A efficient, stable new electrode materials are found, becomes current lithium cell cathode material field and continues to solve The technical issues of.
Summary of the invention
The purpose of the present invention is: lithium cell cathode material energy density is not high enough in the prior art for solution, charge and discharge cycles The technical problem of performance difference, the present invention provides a kind of novel lithium cell cathode material and preparation method thereof, the negative electrode materials Has special pattern, i.e. the tin oxide of expanded graphite area load has cross acicular texture.
In order to achieve the above object, present invention employs following technical solutions.
A kind of expanded graphite negative electrode material loading cross acicular tin oxide, it is characterised in that: including expanded graphite and oxygen Change tin, the tin oxide is distributed in expanded graphite surface in cross is needle-shaped.
As the improved technical solution of the present invention, the Theoretical Mass ratio of the tin oxide and expanded graphite is 1:20~1: 5。
As the improved technical solution of the present invention, the density of the negative electrode material is 0.164~0.518g/cm3, specific surface Product is 100~230m2/g。
It is including as follows the present invention also provides the preparation method of the expanded graphite negative electrode material of load cross acicular tin oxide Step:
Expanded graphite is immersed in the water by S1, is stirred 10min~2h, is obtained expanded graphite suspension;
S2 is prepared and is contained tin-salt solution, then containing structure directing agent is added in tin-salt solution, is dissolved;
S3, by being slowly dropped in expanded graphite suspension containing tin-salt solution containing structure directing agent;
S4, by S3, treated that expanded graphite suspension is heated to reflux 0.5~2h, is cooled to room temperature;
Excessive sodium borohydride alkaline solution is added dropwise in S5 in S4 treated suspension, stirs 2~5h, is made stanniferous The composite material of oxide and expanded graphite;
Composite material containing tin-oxide and expanded graphite made from S6, filtration washing S5, until the pH of filtrate most in Property;
The composite material containing tin-oxide and expanded graphite of S6 processing is heated to 300 by S7 under inert gas protection ~500 DEG C, 1~3h is kept the temperature, the expanded graphite negative electrode material of load cross acicular tin oxide is made.
As the improved technical solution of the present invention, the structure directing agent is ionic polyelectrolyte.
As the improved technical solution of the present invention, the structure directing agent is polyvinylidene base alkyl dimethyl ammonium chloride, polyphenyl Vinyl sulfonic acid potassium or kayexalate.
As the improved technical solution of the present invention, the mass concentration of the expanded graphite is 5~20g/L.
As the improved technical solution of the present invention, the concentration containing tin-salt solution is 0.1~1mol/L, and the structure is led To 5~20:1 of mass ratio of agent and Sn.
The technical solution modified as the present invention, the usage amount of the sodium borohydride alkaline solution are as follows: sodium borohydride and Sn Molar ratio be more than or equal to 0.25:1;The molar ratio of alkali metal hydroxide and Sn are 2~4:1.
As the improved technical solution of the present invention, in final negative electrode material obtained, the theory of tin oxide and expanded graphite Mass ratio is 1:20~1:5.
The utility model has the advantages that
Compared with prior art, lithium cell cathode material provided by the invention has special appearance structure, and has The advantages that energy density is high, charge-discharge performance is good.The analysis of causes is as follows:
1. expanded graphite has pore structure abundant, strong adsorption, electric conductivity is good, resistivity itself is low, and Due to insert and graphite linings interaction and show original graphite and new capability that intercalated material does not have.Expanded graphite With thermal conductivity more better than general graphite and electric conductivity.In expanded graphite meterial, certain metals are selectively mixed, it will Change graphite microstructure and electronic state, enhance the electric conductivity of graphite type material, make electronics more evenly be distributed in graphite The surface of grain reduces polarization, so as to improve its high rate during charging-discharging.
2. containing structure directing agent is added in tin-salt solution, when tin ion and expanded graphite acted on preferably with Expanded graphite lamella combines, and prevents tin ion in the reunion of expanded graphite lamella;When medium temperature is calcined, tin oxide can be guided Crystal carries out ordering growth on expanded graphite surface.
3. tin oxide has higher theoretical capacity in lithium cell cathode material, when tin oxide consolidated with special appearance it is attached On expanded graphite surface, in the lithium intercalation/deintercalation process, expanded graphite buffered stannic oxide materials volume contraction variation, therefore After repeated charge, the negative electrode material that tin oxide is formed with expanded graphite will not rupture, and be not easy to fall off from collector, To significantly improve the charge-discharge performance of negative electrode material.It is not connected to the tin oxide of directed agents guidance, it will expanding Graphite surface is reunited, and attachment is insecure, so as to cause tin oxide/expanded graphite meterial obtained as lithium cell negative pole, just Beginning capacity is high, but chemical property is remarkably decreased after repeated charge.
4. the mass ratio of tin oxide and expanded graphite is too low, the volume energy density of expanded graphite promotes few, tin oxide Excessively high with the mass ratio of expanded graphite, then tin oxide adheres to insecure, its electrochemistry after multiple charge and discharge on expanded graphite surface Performance is remarkably decreased.
Detailed description of the invention
Fig. 1 is the SEM figure of the expanded graphite negative electrode material of the load cross acicular tin oxide obtained of embodiment 5;
Fig. 2 is the figure of tin oxide/exfoliated-graphite composite SEM made from embodiment 9.
Specific embodiment
In order to make it will be apparent to those skilled in that the present invention is legibly understood, now in conjunction with specific embodiment and specification Attached drawing, the present invention is described in detail.
Embodiment 1
S1: expanded graphite is immersed in the water, and is stirred 10min, is obtained the expanded graphite suspension of 5g/L;
S2: for preparing 0.1mol/L contains tin-salt solution, then containing addition structure directing agent polyvinylidene in tin-salt solution Base alkyl dimethyl ammonium chloride, dissolution;The additive amount of the structure directing agent and the mass ratio of tin are 5:1;
S3: the 66.4mL containing tin-salt solution containing structure directing agent is slowly dropped in the expanded graphite suspension of 1L, It is added dropwise in 1min;
S4: by S3, treated that expanded graphite suspension is heated to reflux 0.5h, is cooled to room temperature;
S5: 62.7mg sodium borohydride and 531.2mg sodium hydroxide are dissolved in 10mL water, after being then added drop-wise to S4 processing Suspension in, stir 2h, be made the composite material containing tin-oxide and expanded graphite;
S6: the filtration washing S5 composite material containing tin-oxide and expanded graphite obtained, until the pH of filtrate most in Property;
S7: the composite material containing tin-oxide and expanded graphite of S6 processing is heated to 300 under inert gas protection DEG C, 3h is kept the temperature, the expanded graphite negative electrode material of load cross acicular tin oxide is made.
Embodiment 2
S1: expanded graphite is immersed in the water, and is stirred 30min, is obtained the expanded graphite suspension of 10g/L;
S2: for preparing 0.3mol/L contains tin-salt solution, then containing addition structure directing agent polyvinylidene in tin-salt solution Base alkyl dimethyl ammonium chloride, dissolution;The additive amount of the structure directing agent and the mass ratio of tin are 10:1;
S3: the 22.1mL containing tin-salt solution containing structure directing agent is slowly dropped in the expanded graphite suspension of 1L, It is added dropwise in 1min;
S4: by S3, treated that expanded graphite suspension is heated to reflux 1h, is cooled to room temperature;
S5: 75.3mg sodium borohydride and 796.8mg sodium hydroxide are dissolved in 10mL water, and being then added drop-wise to S4, treated In suspension, 3h is stirred, the composite material containing tin-oxide and expanded graphite is made;
S6: the filtration washing S5 composite material containing tin-oxide and expanded graphite obtained, until the pH of filtrate most in Property;
S7: the composite material containing tin-oxide and expanded graphite of S6 processing is heated to 400 under inert gas protection DEG C, 2h is kept the temperature, the expanded graphite negative electrode material of load cross acicular tin oxide is made.
Embodiment 3
S1: expanded graphite is immersed in the water, and is stirred 1h, is obtained the expanded graphite suspension of 15g/L;
S2: for preparing 0.5mol/L contains tin-salt solution, then containing addition structure directing agent polyvinylidene in tin-salt solution Base alkyl dimethyl ammonium chloride, dissolution;The additive amount of the structure directing agent and the mass ratio of tin are 15:1;
S3: the 13.3mL containing tin-salt solution containing structure directing agent is slowly dropped in the expanded graphite suspension of 1L, It is added dropwise in 30s;
S4: by S3, treated that expanded graphite suspension is heated to reflux 1.5h, is cooled to room temperature;
S5: 75.3mg sodium borohydride and 1062.4mg sodium hydroxide are dissolved in 10mL water, after being then added drop-wise to S4 processing Suspension in, stir 4h, be made the composite material containing tin-oxide and expanded graphite;
S6: the filtration washing S5 composite material containing tin-oxide and expanded graphite obtained, until the pH of filtrate most in Property;
S7: the composite material containing tin-oxide and expanded graphite of S6 processing is heated to 500 under inert gas protection DEG C, 1h is kept the temperature, the expanded graphite negative electrode material of load cross acicular tin oxide is made.
Embodiment 4
S1: expanded graphite is immersed in the water, and is stirred 2h, is obtained the expanded graphite suspension of 20g/L;
S2: for preparing 1mol/L contains tin-salt solution, then containing addition structure directing agent polyvinylidene base in tin-salt solution Alkyl dimethyl ammonium chloride, dissolution;The additive amount of the structure directing agent and the mass ratio of tin are 20:1;
S3: the 6.6mL containing tin-salt solution containing structure directing agent is slowly dropped in the expanded graphite suspension of 1L, It is added dropwise in 30s;
S4: by S3, treated that expanded graphite suspension is heated to reflux 2h, is cooled to room temperature;
S5: 62.7mg sodium borohydride and 796.8mg sodium hydroxide are dissolved in 10mL water, after being then added drop-wise to S4 processing Suspension in, stir 5h, be made the composite material containing tin-oxide and expanded graphite;
S6: the filtration washing S5 composite material containing tin-oxide and expanded graphite obtained, until the pH of filtrate most in Property;
S7: the composite material containing tin-oxide and expanded graphite of S6 processing is heated to 400 under inert gas protection DEG C, 2h is kept the temperature, the expanded graphite negative electrode material of load cross acicular tin oxide is made.
Embodiment 5
S1: expanded graphite is immersed in the water, and is stirred 2h, is obtained the expanded graphite suspension of 10g/L;
S2: for preparing 0.5mol/L contains tin-salt solution, then containing addition structure directing agent polyvinylidene in tin-salt solution Base alkyl dimethyl ammonium chloride, dissolution;The additive amount of the structure directing agent and the mass ratio of tin are 10:1;
S3: the 13.3mL containing tin-salt solution containing structure directing agent is slowly dropped in the expanded graphite suspension of 1L, It is added dropwise in 30s;
S4: by S3, treated that expanded graphite suspension is heated to reflux 1h, is cooled to room temperature;
S5: 62.7mg sodium borohydride and 796.8mg sodium hydroxide are dissolved in 10mL water, after being then added drop-wise to S4 processing Suspension in, stir 4h, be made the composite material containing tin-oxide and expanded graphite;
S6: the filtration washing S5 composite material containing tin-oxide and expanded graphite obtained, until the pH of filtrate most in Property;
S7: the composite material containing tin-oxide and expanded graphite of S6 processing is heated to 400 under inert gas protection DEG C, 2h is kept the temperature, the expanded graphite negative electrode material of load cross acicular tin oxide is made.
Embodiment 6
S1: expanded graphite is immersed in the water, and is stirred 2h, is obtained the expanded graphite suspension of 10g/L;
S2: for preparing 0.5mol/L contains tin-salt solution, then containing addition structure directing agent polyvinylidene in tin-salt solution Base alkyl dimethyl ammonium chloride, dissolution;The additive amount of the structure directing agent and the mass ratio of tin are 10:1;
S3: the 33.2mL containing tin-salt solution containing structure directing agent is slowly dropped in the expanded graphite suspension of 1L, It is added dropwise in 1min;
S4: by S3, treated that expanded graphite suspension is heated to reflux 1h, is cooled to room temperature;
S5: 156.7mg sodium borohydride and 1992mg sodium hydroxide are dissolved in 10mL water, after being then added drop-wise to S4 processing Suspension in, stir 4h, be made the composite material containing tin-oxide and expanded graphite;
S6: the filtration washing S5 composite material containing tin-oxide and expanded graphite obtained, until the pH of filtrate most in Property;
S7: the composite material containing tin-oxide and expanded graphite of S6 processing is heated to 400 under inert gas protection DEG C, 2h is kept the temperature, the expanded graphite negative electrode material of load cross acicular tin oxide is made.
Embodiment 7
S1: expanded graphite is immersed in the water, and is stirred 2h, is obtained the expanded graphite suspension of 10g/L;
S2: for preparing 0.5mol/L contains tin-salt solution, then containing addition structure directing agent polyvinylidene in tin-salt solution Base alkyl dimethyl ammonium chloride, dissolution;The additive amount of the structure directing agent and the mass ratio of tin are 10:1;
S3: the 5.3mL containing tin-salt solution containing structure directing agent is slowly dropped in the expanded graphite suspension of 1L, It is added dropwise in 30s;
S4: by S3, treated that expanded graphite suspension is heated to reflux 1h, is cooled to room temperature;
S5: 25.1mg sodium borohydride and 318.7mg sodium hydroxide are dissolved in 10mL water, and being then added drop-wise to S4, treated In suspension, 4h is stirred, the composite material containing tin-oxide and expanded graphite is made;
S6: the filtration washing S5 composite material containing tin-oxide and expanded graphite obtained, until the pH of filtrate most in Property;
S7: the composite material containing tin-oxide and expanded graphite of S6 processing is heated to 400 under inert gas protection DEG C, 2h is kept the temperature, the expanded graphite negative electrode material of load cross acicular tin oxide is made.
Embodiment 8
S1: expanded graphite is immersed in the water, and is stirred 2h, is obtained the expanded graphite suspension of 10g/L;
S2: for preparing 0.5mol/L contains tin-salt solution, then containing addition structure directing agent polystyrene in tin-salt solution Potassium sulfonate, dissolution;The additive amount of the structure directing agent and the mass ratio of tin are 10:1;
S3: the 13.3mL containing tin-salt solution containing structure directing agent is slowly dropped in the expanded graphite suspension of 1L, It is added dropwise in 30s;
S4: by S3, treated that expanded graphite suspension is heated to reflux 1h, is cooled to room temperature;
S5: 62.7mg sodium borohydride and 796.8mg sodium hydroxide are dissolved in 10mL water, after being then added drop-wise to S4 processing Suspension in, stir 4h, be made the composite material containing tin-oxide and expanded graphite;
S6: the filtration washing S5 composite material containing tin-oxide and expanded graphite obtained, until the pH of filtrate most in Property;
S7: the composite material containing tin-oxide and expanded graphite of S6 processing is heated to 400 under inert gas protection DEG C, 2h is kept the temperature, the expanded graphite negative electrode material of load cross acicular tin oxide is made.
Embodiment 9
S1: expanded graphite is immersed in the water, and is stirred 2h, is obtained the expanded graphite suspension of 10g/L;
S2: for preparing 0.5mol/L contains tin-salt solution;
S3: 13.3mL containing tin-salt solution is slowly dropped in the expanded graphite suspension of 1L, is added dropwise in 30s;
S4: by S3, treated that expanded graphite suspension is heated to reflux 1h, is cooled to room temperature;
S5: 62.7mg sodium borohydride and 796.8mg sodium hydroxide are dissolved in 10mL water, after being then added drop-wise to S4 processing Suspension in, stir 4h, be made the composite material containing tin-oxide and expanded graphite;
S6: the filtration washing S5 composite material containing tin-oxide and expanded graphite obtained, until the pH of filtrate most in Property;
S7: the composite material containing tin-oxide and expanded graphite of S6 processing is heated to 400 under inert gas protection DEG C, 2h is kept the temperature, tin oxide/exfoliated-graphite composite is made.
It will be loaded made from embodiment 1-8 made from the expanded graphite negative electrode material and embodiment 9 of cross acicular tin oxide Tin oxide/exfoliated-graphite composite be assembled into lithium half-cell is measured each material chemical property it is as follows:
Capacity after the density of material made from 1 embodiment 1-9 of table, initial capacity and circulation 50 times and 300 times
Obviously, above-described embodiment is just for the sake of clearly demonstrating example, rather than the limitation to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.As long as being made on the basis of the embodiment of the present invention The change scheme of common-sense, among protection scope of the present invention.

Claims (10)

1. a kind of expanded graphite negative electrode material for loading cross acicular tin oxide, it is characterised in that: including expanded graphite and oxidation Tin, the tin oxide are distributed in expanded graphite surface in cross is needle-shaped.
2. negative electrode material according to claim 1, it is characterised in that: the Theoretical Mass of the tin oxide and expanded graphite ratio For 1:20~1:5.
3. negative electrode material according to claim 2, it is characterised in that: the density of the negative electrode material be 0.164~ 0.518g/cm3, specific surface area is 100~230m2/g。
4. a kind of preparation method for the expanded graphite negative electrode material for loading cross acicular tin oxide, includes the following steps:
Expanded graphite is immersed in the water by S1, is stirred 10min~2h, is obtained expanded graphite suspension;
S2 is prepared and is contained tin-salt solution, then containing structure directing agent is added in tin-salt solution, is dissolved;
S3, by being slowly dropped in expanded graphite suspension containing tin-salt solution containing structure directing agent;
S4, by S3, treated that expanded graphite suspension is heated to reflux 0.5~2h, is cooled to room temperature;
Excessive sodium borohydride alkaline solution is added dropwise in S5 in S4 treated suspension, stirs 2~5h, stanniferous oxidation is made The composite material of object and expanded graphite;
S6 is filtered, washed the composite material containing tin-oxide and expanded graphite made from S5, until the pH of cleaning solution is in neutrality;
The composite material containing tin-oxide and expanded graphite of S6 processing is heated to 300~500 by S7 under inert gas protection DEG C, 1~3h is kept the temperature, the expanded graphite negative electrode material of load cross acicular tin oxide is made.
5. the preparation method according to claim 4, it is characterised in that: the structure directing agent is ionic polyelectrolyte.
6. preparation method according to claim 5, it is characterised in that: the structure directing agent is polyvinylidene base dimethyl Ammonium chloride, polystyrolsulfon acid potassium or kayexalate.
7. the preparation method according to claim 4, it is characterised in that: the mass concentration of the expanded graphite is 5~20g/ L。
8. the preparation method according to claim 4, it is characterised in that: the concentration containing tin-salt solution is 0.1~1mol/ 5~20:1 of mass ratio of L, the structure directing agent and Sn.
9. the preparation method according to claim 4, which is characterized in that the usage amount of the sodium borohydride alkaline solution are as follows: The molar ratio of sodium borohydride and Sn are more than or equal to 0.25:1;The molar ratio of alkali metal hydroxide and Sn are 2~4:1.
10. the preparation method according to claim 4, it is characterised in that: in final negative electrode material obtained, tin oxide with The Theoretical Mass ratio of expanded graphite is 1:20~1:5.
CN201711351875.6A 2017-12-15 2017-12-15 Expanded graphite cathode material loaded with cross needle-shaped tin oxide and preparation method thereof Active CN109935824B (en)

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